Some physical properties of calcia and yttria stabilized ThO2 ceramics

In this paper the density, electrical conductivity, and dielectric permittivity of vacant ceramics of Ca _x Th_1–x O_2–x and Y _x Th_1–x O_2–x /2 type, respectivelly, were investigated as functions of temperature, frequency, and composition of these systems.The density drops with increasing calcium or yttrium amount, respectively. In the ThO₂-CaO system this is in agreement with the mechanism of formation of vacant phase Ca _x Th_1–x O_2x . The decrease of porosity in the ThO₂-Y₂O₃ system with increasing yttrium content can be due various factors which influence the mobility of Y³⁺ ions and, thus, also the formation of pores.The investigation of transport numbers has shown that whilst the Ca _x Th_1–x O_2–x phase under our experimental conditions is essentially p-type conductor, the Y _x Th_1–x O_2–x/2 phase is essentially ionic conductor.The transport of ion carriers is a diffusion-like process which has activation energy 1·28 to 1·16eV in the Ca _x Th_1–x O_2–x phase and 1·28 to 1·06 in the Y _x Th_1–x O_2–x /2 phase, respectively. The association of impurity ions with anion vacancies provides the maxima in conductivity isotherms.The relative dielectric permittivity of the vacant phase Ca _x Th_1–x O_2–x ranges from 19·2 to 36·2, in the phase Y _x Th_1–x O_2–x /2 from 19·2 to 103, depending on temperature, frequency, and composition of these systems.     

Lithium ion conductive glass–ceramics with Li3Fe2(PO4)3 and YAG laser-induced local crystallization in lithium iron phosphate glasses

The glasses with the composition of 37.5Li₂O–(25 − x)Fe₂O₃–xNb₂O₅–37.5P₂O₅ (mol%) (x = 5,10,15) are prepared, and it is found that the addition of Nb₂O₅ is effective for the glass formation in the lithium iron phosphate system. The glass–ceramics consisting of Nasicon-type Li₃Fe₂(PO₄)₃ crystals with an orthorhombic structure are developed through conventional crystallization in an electric furnace, showing electrical conductivities of 3 × 10^− 6 Scm^− 1 at room temperature and the activation energies of 0.48 eV (x = 5) and 0.51 eV (x = 10) for Li⁺ ion conduction in the temperature range of 30–200 °C. A continuous wave Nd:YAG laser (wavelength: 1064 nm) with powers of 0.14–0.30 W and a scanning speed of 10 μm/s is irradiated onto the surface of the glasses, and the formation of Li₃Fe₂(PO₄)₃ crystals is confirmed from XRD analyses and micro-Raman scattering spectra. The crystallization of the precursor glasses is considered as new route for the fabrication of Li₃Fe₂(PO₄)₃ crystals being candidates for use as electrolyte materials in lithium ion secondary batteries.     

Non-superconducting and rendered superconducting YBa2Cu3O7−x . An in-situ photoemission study

We present X-ray photoemission spectroscopy (XPS) results obtained on polycrystalline YBa₂Cu₃O_7–x in the non-metallic (x>0.6) and metallic state (x<0.6) by an in-situ oxygen deloading/loading procedure, thus avoiding uncontrolled surface contaminations. The transition to the metallic (superconducting) state is characterized by corresponding changes in the O1s and Cu2p photoelectron lineshapes being in accordance with charge transfer from CuO₂ planes to CuO chains. In particular, a peak at 531.1 eV binding energy is related to the presence of oxygen hole states (O^–).     

Effect of Y2O3 addition on the conductivity and elastic modulus of (CeO2)1 − x(YO1.5)x

The conductivity and elastic modulus of (CeO₂)_1 − x(YO_1.5)_x for x values of 0.10, 0.15, 0.20, 0.30, and 0.40 were investigated by experiments and molecular dynamics simulations. The calculated conductivity exhibited a maximum value at approximately 15 mol% Y₂O₃; this trend agreed with that of the experimental results. In order to clarify the reason for the occurrence of the maximum conductivity, the paths for the transfer of oxygen vacancies were counted. The numerical result revealed that as the content of Y₂O₃ dopant increases, the number of paths for the transfer of oxygen vacancies decreases, whereas the number of oxygen vacancies for conductivity increases. Thus, the trade-off between the increase in the number of vacancy sites and the decrease in the vacancy transfer was considered to be the reason for the maximum conductivity occurring at the Y₂O₃ dopant content of approximately 15 mol%. The calculated elastic modulus also exhibited a minimum value at approximately 20 mol% Y₂O₃, which also agreed with the experimental results. It was shown that the Y–O–Y bonding energy increased with the increasing content of Y₂O₃ dopant. Thus, the trade-off between the increase in the number of vacancy sites and that in the Y–O–Y bonding energy was considered to be the reason for the minimum elastic modulus occurring at the Y₂O₃ dopant content of approximately 20 mol%.     

Preparation and study of magnetic properties of silico phosphate glass and glass-ceramics having iron and zinc oxide

The magnetic properties of 25SiO₂–50CaO–15P₂O₅–(10−x)Fe₂O₃−xZnO (where x=0, 2, 5 mol%) glass and glass-ceramics have been studied. These glasses are prepared by melt quench technique and heat treated at 800 °C for 6 h. Electron Spectroscopy for Chemical Analysis (ESCA) revealed that the fraction of non-bridging oxygen decreases with the increase in zinc oxide content. Evolution of crystalline phases in glass-ceramics has been studied by X-ray diffraction (XRD). The microstructure as seen by scanning electron microscopy (SEM) exhibits formation of nanosize particles. Effect of controlled heat treatment on magnetic properties was studied by means of a Superconducting Quantum Interference Device (SQUID) magnetometer. Mössbauer spectroscopy at room temperature was also carried out to determine the state of iron ions in glasses and glass-ceramics. Isomer shift values of the glasses suggest that Fe³⁺ and Fe²⁺ are in tetrahedral coordination. The analysis of the glass without ZnO shows about 58 wt% of total iron ions is in the Fe³⁺ state. The samples on heat treatment show improved magnetic properties due to the formation of magnetic nanoparticles. Magnetic studies revealed the relaxation of magnetic particles and the increase in saturation magnetization with addition of 2 mol% ZnO. Increase in ZnO content results in decrease in the strength of dipolar interactions.     

Luminescence from ZnO/MgO nanoparticle structures prepared by solution techniques

The optical and structural properties of mixed ZnO/MgO particles prepared by solution techniques are investigated by the cathodoluminescence and electron microscopy techniques. The samples annealed at 400–1000 °C show well crystalline wurtzite structure of the ZnO (MgZnO) particles with the size in range of 10–100 nm. Annealing at high temperatures (>700 °C) leads to Mg diffusion in ZnO and Mg_xZn_1−xO alloy formation. The blue shifts of the near-band-edge emission as a result of the alloy band gap widening and quantum confinement effect for the small size particles are demonstrated.     

Effect of substrate temperature on the morphology, structural and optical properties of Zn1−xCoxO thin films

Zn_1−xCo_xO thin films with c-axis preferred orientation were deposited on sapphire (0 0 0 1) by pulsed laser deposition (PLD) technique at different substrate temperatures in an oxygen-deficient ambient. The effect of substrate temperature on the microstructure, morphology and the optical properties of the Zn_1−xCo_xO thin films was studied by means of X-ray diffraction (XRD), atomic force microscopy (AFM), UV-visible-NIR spectrophotometer, fluorescence spectrophotometer. The results showed that the crystallization of the films was promoted as substrate temperature rose. The structure of the samples was not distorted by the Co incorporating into ZnO lattice. The surface roughness of all samples decreased as substrate temperature increased. The Co concentration in the film was higher than in the target. Emission peak near band edge emission of ZnO from the PL spectra of the all samples was quenched because the dopant complexes acted as non-radiative centers. While three emission bands located at 409 nm (3.03 eV), 496 nm (2.5 eV) and 513 nm (2.4 eV) were, respectively, observed from the PL spectra of the four samples. The three emission bands were in relation to Zn interstitials, Zn vacancies and the complex of V_O and Zn_i (V_OZn_i). The quantity of the Zn interstitials maintained invariable basically, while the quantity of the V_OZn_i slightly decreased as substrate temperature increased.     

X-ray photoelectron spectroscopy of the high-temperature superconductor YBa2Cu3O7−x and the copper oxides

The X-ray photoelectron (XPS) core-level spectra of Cu-metal, Cu₂O, CuO, NaCuO₂ and YBa₂Cu₃O_7–x have been determined. It has been shown, that the Cu³⁺ ions in NaCuO₂ are reduced to lower valence states by X-rays in ultrahigh vacuum (UHV). The determination of the electron binding energy of the Cu 2 _{p 3/2} level in NaCuO₂ yields a value of 934.1 eV. The shape of the Cu 2 _{p 3/2} peak as well as the appearence of a shake-up satellite in YBa₂Cu₃O_7–x which is smaller than in CuO show that YBa₂Cu₃O_7–x contains Cu³⁺ ions. The behaviour of YBa₂Cu₃O_7–x also was studied during X-ray irradiation and a reduction was noticeable.     

On the paramagnetic behavior of heavily doped Zn1−xMnxO films fabricated by Pechini’s method

Heavily doped Zn_1−xMn_xO (x = 0.3) films were prepared by polymeric precursor method onto glass substrates and their structural, morphological, optical and magnetic properties carefully studied. Undoped ZnO films were also prepared for the purpose of comparison. The polymeric precursor method consists in preparing a coating solution from the Pechini process followed by a three-step thermal treatment of the as deposited films at temperatures up to 550 °C for 30 min. X-ray diffraction (XRD) analysis reveals the typical hexagonal wurtzite structure of the undoped ZnO film. The addition of Mn ions leads to a dramatic reduction of the crystalline quality of film although no evidence of affectation by secondary phases is found. The affectation of the ZnO structure may be due to the formation of Mn clusters and generation of defects such as vacancies and interstitials. Here, the solubility limit of the Mn ions in ZnO should play an important role and it is discussed in the framework of ionic radius and valence states. The scanning electron microscopy (SEM) analysis shows that the surface of the doped sample was affected by the presence of cracks due, probably, to the expansion of the lattice constant of Zn_0.7Mn_0.3O caused by the Mn incorporation in the ZnO lattice. The existence of cluster-type structures on the surface is corroborated by atomic force microscopy (AFM). The EDX analysis, carried out on some areas in the film, yielded Mn/Zn ratios of about 0.3, which points out to an effective Mn incorporation in the film. On the other hand, the absorption edge of the doped films is red shifted to 2.9 eV (3.24 eV for undoped ZnO film) and the absorption edge is less sharp due, probably, to amorphous states appearing in the band gap. No evidence of dilute magnetic semiconductor mean-field ferromagnetic behavior is observed. The temperature dependence of the magnetization follows a Curie law suggesting pure paramagnetic behavior. The very small s-shape behavior of M versus H (without hysteresis) observed at room temperature on selected areas would stem from Mn clusters which are easily formed in transition metal doped ZnO.     

Room-temperature ferromagnetism in lightly Cr-doped ZnO nanoparticles

Zn_1−x Cr _x O (0≤x≤0.15) nanoparticles were synthesized by an auto-combustion method and characterized by x-ray diffraction and Raman scattering techniques. The solubility limit for Cr in ZnO was determined as x≈0.03. Room-temperature ferromagnetism (RT-FM) was observed in lightly Cr-doped ZnO nanoparticles with x=0.01 and 0.02. Raman scattering spectra of the lightly Cr-doped and Co-doped ZnO were studied and compared. The enhancement of both the magnetization and the intensity of Raman scattering peak associated with donor defects (Zn_i and/or V_O) and carriers indicates that light Cr doping in ZnO could be an effective way to achieve pronounced RT-FM and the ferromagnetism is closely related to the dopant-donor hybridization besides the ferromagnetic Cr–O–Cr superexchange interactions.     

Influence of Oxygen Vacancies on the Luminescence Spectra of Y2O3 Thin Films

Luminescence spectra of Y₂O₃ thin films annealed in air and in vacuum are investigated. It is established that the presence of oxygen vacancies leads to a decrease in the intensity of the luminescence band with a maximum at 3.4 eV (related to emission of selflocalized Frenkel excitons describing the excited state of a molecular ion (YO₆)^9–) and of the luminescence band with a maximum at 2.9 eV (related to the anion sublattice). It is revealed that the oxygen vacancies also lead to a decrease in the luminescence intensity in the 2.60, 2.35, 2.10. 1.90, and 1.70 eV bands that are related to radiative recombination in the donor–acceptor Y³⁺–O^2– pairs. The donor–acceptor distances are calculated.     

制备工艺对Zn1-xMgxO薄膜结构及光学性能的影响

采用脉冲激光沉积（PLD）方法在单晶Si（100）衬底上沿c轴方向生长单晶Zn_1-xMg_xO薄膜,通过X射线衍射（XRD）、原子力显微镜（AFM）、扫描电镜（SEM）和荧光光谱（PL）研究了膜厚、Mg含量、退火温度及氧气氛等制备工艺对Zn_1-xMg_xO薄膜的结构、形貌和光学性质的影响.实验结果表明,Mg含量x≤0.15时, Zn_{关键词： 1-x}Mg_xO薄膜')" href="#">Zn_1-xMg_xO薄膜 制备工艺 结构 光学性质     

Growth of wide band gap wurtzite ZnMgO layers on (0001) Al2O3 by radical-source molecular beam epitaxy

Wurtzite structure ZnMgO layers have been grown using radical-source molecular beam epitaxy on high-quality ZnO buffer layers grown on (0001) sapphire substrates. The thickness of the ZnO buffer layers is 300 nm, with full width at half maxim of the HR-XRD (0002) rocking curves as low as 25 arcsec. In-situ Reflection High-Energy Electron Diffraction (RHEED) was employed for the optimization of the ZnMgO growth. RHEED and X-Ray Diffractometry measurements did not reveal any phase change from the wurzite structure to the rocksalt structure. The C-lattice parameter of Zn_1−xMg_xO films decreased from 5.209 to 5.176 Å with increasing x to 0.2. The surface morphology of the samples was studied with atomic force microscopy. The root mean square roughness values of 200 nm thick ZnMgO (x=0.2) was less than 1 nm. The main photoluminescence peak of Zn_1−xMg_xO shifted to as high as 3.77 eV owing to the increasing Mg composition of up to x=0.2.     

Band alignment at sputtered ZnSx O1–x/Cu(In,Ga)(Se,S)2 heterojunctions

Valence band offsets ΔE_VBM at ZnS_x O_1–x/Cu(In,Ga)(Se,S)₂ (CIGSSe) heterojunctions have been studied by photoemission spectroscopy (XPS, UPS) as a function of composition x in sputtered ZnS_x O_1–x films. In the composition range from ZnO to ZnS we found ΔE_VBM between –(2.1 ± 0.3) eV and –(0.8 ± 0.4) eV, respectively. Considering the optical band gaps, the conduction band offsets ΔE_CBM range from –(0.1 ± 0.3) eV to +(1.4 ± 0.4) eV. These results suggest that sputtered ZnS_x O_1–x is suitable as substitution for the CdS buffer and ZnO window layers in standard chalcopyrite‐based solar cells. Current–voltage characteristics of the solar cells have been investigated as a function of the composition x. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Photoinduced non-linear optical diagnostic of SiNxOy/Si111 interfaces

Anisotropic (elliptically polarized) photoinduced second harmonic generation (PISHG) in SiN_xO_y/Si1 1 1 films was proposed for contact-less monitoring of specimens with different nitrogen to oxygen (N/O) ratios. As a source for the photoinducing light, we used a nitrogen Q-switched pulse laser at wavelengths of 315, 337 and 354 nm as well as doubled frequency YAG–Nd laser wavelength (λ=530 nm). The YAG : Nd pulse laser (λ=1.06 μm; W=30 MW; τ=10–50 ps) was used to measure the PISHG. All measurements were done in a reflected light regime. We found that the output PISHG signal was sensitive to the N/O ratio and the film thickness. Measurements of the PISHG versus pumping wavelengths, powers, incident angles as well as independent measurements of the DC-electric field induced second harmonic generation indicate the major role played in this process by axially symmetric photoexcited electron–phonon states. The SiN_xO_y films were synthesized using a technique of chemical evaporation at low pressures. Films with thickness varying between 10 and 30 nm and with an N/O ratio between 0 and 1 were obtained. Electrostatic potential distribution at the Si1 1 1–SiN_xO_y interfaces was calculated. Comparison of the experimentally obtained and quantum chemically calculated PISHG data are presented. High sensitivity of anisotropic PISHG to the N/O ratio and film thickness is revealed. The role of the electron–phonon interactions in the dependencies observed is discussed. We have shown that the PISHG method has higher sensitivity than the traditional extended X-ray absorption fine structure spectroscopic and linear optical method for films with the N/O ratio higher than 0.50.     

X-ray photoelectron spectroscopy study of Pd oxidation by RF discharge in oxygen

The low-temperature oxidation of polycrystalline palladium by RF oxygen plasma was studied via X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Detailed information about the electronic states of palladium and oxygen was obtained based on the XPS curve fitting analysis of Pd3d and Pd3p + O1s lines. The results showed that Pd oxidation by oxygen plasma was different from Pd oxidation in pure O₂ at high temperature. SEM shows well-structured submicron PdO particles result from oxidation in pure O₂, whereas plasma oxidation results in the predominant formation of two-dimensional PdO structures covering the initial crystallites of the Pd foil. Further oxidation to a three-dimensional PdO phase occurs under prolonged treatment with oxygen plasma. The formation of a PdO_x (x > 1) species, characterized by a E_b(Pd3d_5/2) = 338.0–338.2 eV value that is close to the Pd⁴⁺ oxidation state, was also observed. This PdO_x species was found to have low thermal stability (T < 400 K). It is proposed that the PdO_x species can be localized within the boundaries of crystallites.     

First-principles calculations of the optical band-gaps of ZnxCd1−xO alloys

Using first-principles calculations, we investigated the structural and electronic properties of two binaries: ZnO in wurtzite structure and CdO in wurtzite and rock-salt structures. In addition several compositions with various ordered structures of Zn_xCd_1−xO alloys were studied within the theory of order–disorder transformation. The full potential linearized augmented plane wave method was used and the d orbitals of Zn and Cd were included in the valence bands. In this investigation of alloying ZnO with CdO, the fundamental band-gap of the alloys is shown to be direct and to decrease versus the Cd composition.     

On the role of Fe2+ ions and cation vacancies in the disaccommodation of ferrites

A study was made of the disaccommodation spectrum of ferrites Mn _x Fe _3–x O _4+y , x>1, in a temperature range above 0°C. A comparison with analogous spectra of ferrites rich in iron (x<1), which contain Fe²⁺ ions in addition to cation vacancies, shows that the disaccommodation maximum around room temperature, observed in iron rich ferrites, is subject to the presence of Fe²⁺ ions. On the other hand, the processes taking place at higher temperatures seem to be substantially common to both types of ferrites and are dependent only on the presence of vacancies.     

Characterization of N-doped ZnO layers grown on (0 0 0 1) GaN/Al2O3 substrates by molecular beam epitaxy

We investigated the optical properties and electrical properties of N-doped ZnO layers grown on (0 0 0 1) GaN/Al₂O₃ substrates by molecular beam epitaxy, employing 10 K photoluminescence (PL) measurements, current–voltage (IV) measurements, capacitance–voltage (CV) measurements, and 100 K photocapacitance (PHCAP) measurements. 10 K PL spectra showed that excitonic emission is dominant in N-doped ZnO layers grown after O-plasma exposure, while overall PL emission intensity is significantly reduced and deep level emission at around 2.0 2.2 eV is dominant in N-doped ZnO layers grown after Zn exposure. IV and CV measurements showed that N-doped ZnO layers grown after Zn exposure have better Schottky diode characteristics than O-plasma exposed samples, and an N-doped ZnO layer grown at 300 °C after Zn exposure has best Schottky diode characteristics. This phenomenon is presumably due to lowered background electron concentration induced by the incorporation of N. PHCAP measurements for the N-doped ZnO layer revealed several midgap trap centers at 1.2 1.8 eV below conduction band minimum.     

Influence of Sr doping on the free carrier absorption in high-T c superconductors La2−x SrxCuO4

The reflectance spectra of polycrystalline La_2–x Sr _x CuO₄ samples were investigated in the energy range between 50 meV and 4 eV in dependence of the Sr content. The spectra are attributed to free carrier absorption of the Drude type, superimposed by optical phonon excitations below 0.1 eV and intrinsic absorption above 1 eV. From the influence of Sr doping onto the plasma energy it is deduced that La_2–x Sr _x CuO₄ is ap-type conductor with a maximum carrier concentration of 2.0×10²¹ cm^–3 forx=0.15. The results are interpreted in terms of a Hubbard model with an empty upper and ap-doped lower Hubbard band with a width of 1.9 eV.